Effect of acetonitrile–water mixtures on the reaction of dinitrochlorobenzene and dinitrochlorobenzotrifluoride with hydroxide ion

The kinetics of alkaline hydrolysis of 2‐chloro‐3,5‐dinitrobenzotrifluoride 1 and 1‐chloro‐2,4‐dinitrobenzene 2 were studied in various acetonitrile–water (AN–H 2 O) mixtures (10–90% w/w) at different temperatures. Thermodynamic parameters Δ H # and Δ S # show great variation, whereas Δ G # appears to vary little with the solvent composition presumably due to compensating variations. The results are discussed in terms of the solvent parameters such as preferential solvation, dielectric constant, polarity/polarizability, and hydrogen bond donor and acceptor parameters. It has been found that the factors controlling the reaction rates are the desolvation of OH − , the solvophobicity of the medium, and free water molecules in rich AN mixed solvent. The data showed that the solvatochromic parameters of (AN–H 2 O) mixed solvent are destroyed in the presence of excess OH − . © 2010 Wiley Periodicals, Inc. Int J Chem Kinet 42: 453–463, 2010